CN1360625A - Non-toxic, microbicidal detergent - Google Patents

Abstract

The invention relates to a non-toxic detergent with biocidal and stain-removing properties which is used in conjunction with a solvent and which contains at least one surface-active agent. Said detergent is characterised in that it contains particles of biological glass which release preferably more than 250 mu g alkali ions and/or alkaline-earth ions per g of glass. Detergents of this type are particularly suitable both for cleaning surfaces and textiles and for use as dishwashing detergents, preferably in the clinical sector and the catering industry.

Description

non-toxic germicidal detergent

The present invention relates to a non-toxic fabric-protecting detergent with bactericidal effect, especially for textiles, and also relates to its preparation method and application.

Detergents are generally compositions comprising a surface-active medium capable of dissolving soils in solvents, especially aqueous solvents. Since most soils contain fat or have fat-like properties, surface-active media, especially surfactants, are used for removal. However, only fatty soils can be removed with this method. Other types of soils such as proteinaceous or proteinaceous soils such as bloodstains, colored substances such as coffee or tea and invisible soils, especially microorganisms, are not easily removed by this method. For this purpose, detergents usually also contain at least one bleaching agent and/or at least one disinfectant in order to remove residual dirt, at least no longer visually. After removing fatty and colored soils, remove stains with oxidation.

Finally, chlorine-releasing chemicals are often used, which also act as disinfectants due to their high oxidizing power. However, this oxidation often only removes the colored portion of the stain, other insoluble matter still contaminates the base material. However, due to its high reactivity, chlorine bleach has the disadvantage of attacking colored textiles and, in many cases, changing their color or causing fading. In addition, aggressive chlorine bleaches attack the materials to be washed, especially textiles, so that after many washes their basic structure is destroyed, which reduces their strength.

For this reason, attempts have been made in the past to accomplish oxidative bleaching using acetic acid. Although the acid itself is sufficiently disinfecting, its poor penetration of porous materials, especially in the case of textiles, results in insufficient disinfection. Also, like chlorine bleach, peracetic acid is formed in detergents from perborate and decomposed acyl groups, so it acts as an oxidizer, albeit to a lesser extent.

This oxidation, while adequate for bleaching of colored stains and milder on many materials than other bleaches, does not achieve adequate disinfection in all cases. For example, aerobic spore formers cannot be removed. In addition, the use of each acid can cause significant damage to woolen fabrics.

Finally, peroxygen compounds react with proteinaceous soils, causing protein aging, especially in the case of bloodstains. However, aged proteins are more or less not completely removed by detergents when they are washed for the usual time.

It is therefore an object of the present invention to provide a detergent which, in addition to having good cleaning properties, also has a disinfecting effect and which is itself non-toxic.

Bioactive glasses have been known for a long time, e.g. Larry L. Hench and John K. West in "Biological Applications of Bioactive Glasses", Biochemical Reports 1996, Volume 13, P.187-241 or in "Bioceramic Concepts" This is reviewed in World Science, edited by L. Hench and J. Wilson, New Jersey (1993). Bioactive glass is characterized by being soluble in aqueous media and forming a layer of hydroxyapatite on the surface, compared to usual glass. Commonly used bioactive glass is either prepared as molten glass or it is so-called sol-gel glass, molten glass has much lower _SiO2 content and much higher sodium content than usual window glass or bottle glass, compared with molten glass In contrast, sol-gel glasses have a high silica content and contain little or no sodium.

The basic properties of bioactive glasses are known to the skilled person, as described in US-A-5074916. Thus, bioactive glass differs from conventional calcium-sodium-silica glass in that it can bind to biological tissue.

Such bioactive glasses can be used, for example, in the treatment of damaged bones, in particular as synthetic bone implants. Furthermore, they are being used successfully in the treatment of chronic wounds, especially ulcers in diabetic patients and tenderness and bedsores in elderly patients. For example, John E. Rectenwald, Sean Lee, and Lyle L. Moldawer et al. (Infection and Immunity, for publication) have shown that in mice, bioactive glass plays an anti-inflammatory role, which is due to the promotion of interleukin -6 (IL-6) activity, and at the same time inhibited the cytokines TNF-α, IL-1-α and IL-10 that increase inflammation, and MPO (myeloperoxidase) (see the 19th Annual Society of Surgical Infection Meeting, 1999, April 28-May 1, 1999).

Furthermore, by E.Allen et al. (Eastman Periodontics School of Dentistry Department of Microbiology) report, the bioactive glass 45-S-5 that obtains by American biomaterials company, FL32615 is the bioactive glass 45-S-5 of the trade mark that is Bioglas ^® has antibacterial effect, this It is not available in ordinary glass pellets (window glass).

However, this bioactive glass releases a large amount of Ca ²⁺ ions. Consequently, a significant increase in water hardness is expected, which in turn leads to increased calcium deposition and reduced detergency, making them unsuitable for use in detergents.

Furthermore, the abrasive action of the glass particles is also expected to cause mechanical damage to the material, in particular to damage to textiles.

Surprisingly, we have found that the above objects can be achieved by means of detergents containing bioactive glass particles. Such particles preferably have a solubility greater than 250 µg alkali metal ion/g glass, the term "alkali metal ion" including alkaline earth metal ions.

Unexpectedly, we found that detergents containing such glass particles not only act as biocides against viruses and bacteria, but are also mild to skin and fabrics, do not cause allergic reactions, and moreover, remove difficult-to-remove stains such as aging of protein. Unexpectedly, the release of alkali metal ions and especially alkaline earth metal ions such as Ca ²⁺ and Mg ²⁺ did not reduce the washing action nor increase the deposition of calcium. Furthermore, the added glass particles do not cause apprehensive damage or damage to the material to be cleaned, especially textiles.

Accordingly, the present invention relates to a non-toxic detergent having biocidal and detersive properties for use with a solvent comprising at least one surfactant. The invention is characterized in that the detergent contains glass particles capable of releasing more than 250 μg of alkali metal ions or alkaline earth metal ions per gram of glass particles and/or in aqueous solutions, in particular physiological aqueous solutions, which form hydroxyl phosphorus on their surface Gray stone layer. Preferably, the glass particles included in the detergent are capable of releasing more than 300 μg, especially more than 500 μg, of alkali metal ions per gram. Particular preference is given to glass particles capable of releasing more than 1 mg of alkali metal ions/alkaline earth metal ions per gram of glass.

This detergent is suitable not only for cleaning and disinfecting surfaces and surgical instruments, but also for textile materials, especially in hospitals and clinics as well as food service centers.

The detergents according to the invention are also particularly suitable as dishwashing agents, especially for dishwashers.

The bioactive glasses encompassed by the invention are preferably conventional bioactive glasses known to the skilled person. Such glasses contain a maximum of 60% by weight of _SiO2 , high levels of _Na2O and CaO, and phosphorus with a high molar ratio of calcium:phosphorus, mostly but not necessarily about 5. If the bioactive glass comes into contact with water or body fluids, it exhibits a specific reaction in which the sodium and calcium ions of the glass displace the H ⁺ ions in solution in a cation exchange reaction, thereby forming a silanol-containing surface on which Sodium hydroxide and calcium hydroxide are associated. An increase in the concentration of hydroxyl ions leads to further reactions with the silicon network at the glass surface, thereby forming additional silanol groups which can be located deeper in the glass.

Because of the high alkaline pH in the glass space, a mixed hydroxyapatite phase is formed from CaO and _P2O5 , which _crystallizes on the _SiO2 surface and interacts with glycosaminoglycans, collagen and Glycoprotein binding.

The calcium:phosphorous molar ratio is preferably >2, especially >3, and preferably <30, especially <20, and a ratio of less than 10 is particularly preferred.

Detergents containing bioactive glass particles particularly preferably contain SiO ₂ , CaO, Na ₂ O, P ₂ O ₅ , CaF ₂ , B ₂ O ₃ , K ₂ O and/or MgO. If the detergent contains bioactive glass particles consisting of molten glass, preferably 40-60% by weight _SiO2 , 10-30% by weight CaO, 10-35% by weight _Na2O , based on the total weight of the glass , 2-8% by weight of P ₂ O ₅ , 0-25% by weight of CaF ₂ , 0-10% by weight of B ₂ O ₃ , 0-8% by weight of K ₂ O and/or 0-5% by weight of MgO . If the bioglass is molten glass, the upper limit of _SiO2 contained is about 60 wt%, preferably about 55 wt%, and the upper limit of 50 wt% is preferred. The content of sodium oxide is preferably greater than 15% by weight, in particular greater than 18% by weight. A sodium oxide content of more than 20% by weight is particularly preferred.

If the bioactive glass contained in the detergent according to the invention is a bioactive glass produced by the sol-gel-method, its silicon oxide content is significantly higher than in molten glass, and its sodium oxide content can be 0. The bioactive glass produced by the sol-gel method preferably contains 40-90% by weight SiO ₂ , 4-45% by weight CaO, 0-10% by weight Na ₂ O, 2-6% by weight P ₂ O ₅ , 0-25% by weight of CaF ₂ , 0-4% by weight of B ₂ O ₃ , 0-8% by weight of K ₂ O and/or 0-5% by weight of MgO.

In the above two types of bioactive glasses, the content of phosphorus oxide is preferably at least 2% by weight, especially at least 4% by weight.

The average particle size d ₅₀ of the microbicidal glass particles in the detergents according to the invention is ≤400 μm, in particular ≤250 μm, with a particle size of ≤100 μm being particularly preferred. Basically higher surface:weight or surface:volume ratios have higher biocidal and disinfectant activity than larger particles. For example particles with a particle size of <50 μm, especially <20 μm or <10 μm give exceptionally high biocidal activity, particles <5 μm being particularly preferred.

However, it has been found that, in the practical range, glass particles with a particle size of 2-60 μm, in particular 2-50 μm and preferably 2-20 μm, increase the mechanical removal of dirt particles due to their frictional action and thus significantly increase the cleaning action.

In addition, the detergent of the present invention exhibits a protein-degrading, ie, protein-dissolving effect. This effect was also confirmed with aged proteins, ie denatured proteins.

The cleaning agent of the present invention can realize the required disinfection and germicidal effects without adding other additives, especially without adding additives capable of releasing Ag ⁺ , Cu ⁺ , Cu ²⁺ and/or Zn ⁺ . However, these additives are required to achieve a synergistic effect. The biocidal activity of the detergents according to the invention can be synergistically increased by adding other disinfecting and germicidal agents which have antibacterial action.

Although it was expected that the incorporation of the glass particles of the present invention into detergents, especially for water containing calcium, would require the addition of large amounts of complexing agents to prevent deposition of calcium and dirt on the material being cleaned, unexpectedly It has been found that the addition of calcium removers such as complexing agents, eg polyphosphates, can be significantly reduced or eliminated without the dreaded calcium deposits. Furthermore, any calcium deposits present are removed due to the frictional action of the glass particles.

In a preferred embodiment of the invention, the detergent according to the invention contains glass particles in an amount of up to 20% by weight or up to 10% by weight, preferably up to 7% by weight and in particular up to 5% by weight, on a dry basis. A minimum amount of 0.01% by weight, especially 0.1% by weight, at least 0.5% by weight or 1% by weight is particularly preferred. Usually the content is 1-4% by weight.

The invention also relates to a method for the preparation of such a detergent, which is characterized in that a surface-active medium, in particular a mixture of different surface-active mediums, especially a surfactant, is mixed with the aforementioned glass particles, and the mixture can also be Solvent dilution.

The invention also relates to the use of the detergent for cleaning surfaces, surgical instruments and beverage bottles and as or in dishwashing agents. Additional special applications include cleaning textiles, especially those used in medical centers, hospital staff and food service centers.

Claims (12)

1. non-toxic detergent, it has the thing of killing livestock and crude removal characteristic, and unites use with solvent, and this washing composition contains at least a surface activating agent, it is characterized in that, and it comprises bioactive glass particle.

2. the washing composition of claim 1 is characterized in that, every gram glass particle of this bioactivity glass discharges at least 300 μ g alkalimetal ions.

3. the washing composition of claim 1 is characterized in that, the mean particle size of glass particle＜400 μ m.

4. the washing composition of one of aforesaid right requirement is characterized in that the mean particle size of glass particle＜100 μ m.

5. the washing composition of one of aforesaid right requirement is characterized in that it contains tensio-active agent as surface activating agent.

6. the washing composition of one of aforesaid right requirement is characterized in that bioactivity glass contains the SiO of 40-60 weight % ₂, the CaO of 10-30 weight %, the Na of 10-35 weight % ₂The P of O, 2-8 weight % ₂O ₅, 0-25 weight % CaF ₂, 0-10 weight % B ₂O ₃, 0-8 weight % K ₂The MgO of O and 0-5 weight %.

7. the washing composition of one of aforesaid right requirement is characterized in that it contains the bioactivity glass by the 1-7 weight % of solid amount.

8. a method that is used for preparing the washing composition of one of claim 1-7 is characterized in that at least a surface activating agent is added in the bioactivity glass, and every gram bioactivity glass can discharge the alkalimetal ion of at least 250 μ g.

9. the application of washing composition in cleaning of objects and/or surface one of among the claim 1-8.

10. the application of claim 9 is characterized in that, this object is a textile materials.

11. claim 9 is as the application of dishwasher detergent.

12. the application that claim 1-11 is used to wash at medical and food service center.